US6103652A - Staged combustion process and apparatus for regenerating a reforming or aromatic compound production catalyst in a moving bed - Google Patents

Staged combustion process and apparatus for regenerating a reforming or aromatic compound production catalyst in a moving bed Download PDF

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US6103652A
US6103652A US09/059,292 US5929298A US6103652A US 6103652 A US6103652 A US 6103652A US 5929298 A US5929298 A US 5929298A US 6103652 A US6103652 A US 6103652A
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combustion
gas
catalyst
oxygen
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François-Xavier Brunet
Emmanuelle Bromet
Jean-Marie Deves
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IFP Energies Nouvelles IFPEN
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • B01J38/14Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/12Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • B01J23/96Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28Regeneration or reactivation
    • B01J27/32Regeneration or reactivation of catalysts comprising compounds of halogens
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/02Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • B01J38/20Plural distinct oxidation stages
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • B01J38/22Moving bed, e.g. vertically or horizontally moving bulk
    • B01J38/24Moving bed, e.g. vertically or horizontally moving bulk having mainly transverse, i.e. lateral, flow of oxygen-containing gas and material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/42Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
    • B01J38/44Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material and adding simultaneously or subsequently free oxygen; using oxyhalogen compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00Reforming naphtha
    • C10G35/04Catalytic reforming
    • C10G35/10Catalytic reforming with moving catalysts
    • C10G35/12Catalytic reforming with moving catalysts according to the "moving-bed" method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00164Controlling or regulating processes controlling the flow
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00184Controlling or regulating processes controlling the weight of reactants in the reactor vessel

Definitions

  • the invention relates to moving bed processes for the production of aromatic compounds, in particular for reforming. More particularly, it concerns the combustion step used during regeneration of a used catalyst and is intended to restore its initial catalytic performances.
  • the catalyst generally comprises a support (for example, formed from at least one refractory oxide, the support possibly also including one or more zeolites), at least one noble metal (preferably platinum), and preferably at least one promoter metal (for example tin or rhenium), at least one halogen and optionally one or more additional elements (such as alkalis, alkaline-earths, lanthanides, silicon, group IVB elements, non noble metals, group IIIA elements, etc.).
  • Catalysts of this type contain platinum, for example, and at least one other metal deposited on a chlorinated alumina support.
  • Such catalysts are used to convert naphthenic or paraffinic hydrocarbons, which can be transformed by dehydrocyclisation and/or dehydrogenation, for reforming or for the production of aromatic compounds (for example for the production of benzene, toluene, ortho-meta- or para-xylenes).
  • aromatic compounds for example for the production of benzene, toluene, ortho-meta- or para-xylenes.
  • Such hydrocarbons originate from fractionation of crude oil by distillation or other transformation processes.
  • reforming reactions were carried out at 40 bars 30 years ago; 20 years ago, at 15 bars.
  • reforming reactors usually operate at pressures of less than 10 bars, in particular in the range 3 to 8 bars.
  • Coke a high molecular weight compound constituted essentially by carbon and hydrogen
  • the H/C molar ratio of the coke formed varies from about 0.3 to 1.0.
  • the carbon and hydrogen atoms form condensed poly-aromatic structures with a variable degree of crystalline organisation, depending on the function and nature of the catalyst and the operating conditions of the reactors. While the selectivity of transformation of the hydrocarbons to coke is very tow, the amounts of coke accumulated on the catalyst can be large. Typically, for fixed bed units, such amounts are in the range 2.0% to 20.0% to 25.5% by weight. For circulating bed units, such amounts are below 10.0% by weight.
  • Coke deposition which is more rapid at low pressure, also requires more rapid regeneration of the catalyst. Current regeneration cycles have become as short as 2-3 days.
  • EP-A-0 378 482 discloses a continuous process for regenerating a reforming or aromatic compound production catalyst which can overcome the inherent disadvantages of shorter and shorter cycles.
  • One of the regeneration steps is oxychlorination of the catalyst.
  • the present invention concerns this step.
  • the used catalyst slowly travels from top to bottom in a regeneration vessel where it meets, in succession, a first radial moving bed combustion zone, a second radial moving bed combustion zone, an axial moving bed oxychlorination zone and an axial moving bed calcining zone, and:
  • the catalyst is treated at a pressure of 3 to 8 bars, substantially equal to that in the first reforming reactor, at a temperature in the range 350° C. to 450° C., using a combustion gas based on an inert gas circulating as a co-current to the catalyst, comprising 0.01% to 1% of oxygen by volume, the combustion gas originating from a zone for washing the gases from the combustion, oxychlorination and calcining steps;
  • the catalyst arriving directly from the first combustion zone is treated at a pressure of 3 to 8 bars, substantially equal to that in the first reactor, at a temperature which is higher by at least 20° C. than the temperature in the first combustion zone, in the presence of gases originating from the first combustion zone and in the presence of an inert makeup gas to which up to 20% by volume of oxygen is added so that the catalyst is in contact with a gas comprising 0.01% to 1% by volume of oxygen, the gases circulating as a co-current with the catalyst.
  • the catalyst is then sent to the oxychlorination zone.
  • FIG. 1 shows a figure from EP-A-0 378 482 which shows the catalyst supplied via pipe (17a), stored in zone (20) then passing to the regeneration stage via pipes (9) into a first combustion zone (101) then into a second combustion zone (105).
  • Combustion is carried out by injecting a gas charged with oxygen (0.01-1% by volume) and if necessary, a supplemental supply (104) of an inert gas charged with oxygen or air.
  • the combustion step ensemble corresponds to part A of FIG. 1.
  • the process of the invention is a process for regenerating a moving bed of catalyst for reforming or for aromatic hydrocarbon production, the catalyst comprising a support, at least one noble metal and at least one halogen, the process comprising a combustion step treating the catalyst in at least two successive combustion zones, the process being characterized in that:
  • each combustion zone is separated from the adjacent combustion zones so as to allow catalyst to pass and to prevent the passage of gas;
  • At least one oxygen-containing gas is introduced into each zone, and the gases produced are extracted from each zone;
  • At least a portion, preferably all, of the gas extracted from one combustion zone is sent to the next zone (in the direction of catalyst flow) with possible oxygen addition (air, for example).
  • the operating conditions are rendered more severe by increasing the temperature and/or the oxygen content of the incoming gas.
  • the oxygen content in the incoming gas is in the range 0.01% to 2%
  • the temperature of the inlet gas is in the range 350-600° C.
  • the residence time of the catalyst in one zone is in the range 5 min to 3 hours
  • the WHSV hourly mass flow rate of gas/mass of catalyst in contact with the gas
  • the combustion step advantageously ends with a final zone for controlling and monitoring combustion completion in which the oxygen consumption is approximately less than 10% of the oxygen entering that zone.
  • the temperature is preferably substantially constant.
  • the monitoring and control zone is preferably located in the lower portion of the last combustion zone, thus after the flame front.
  • a gas containing oxygen in an amount which is higher than that of the gas entering the upstream levels (in the direction of flow of the catalyst) is introduced into the control and monitoring zone.
  • the present invention defines combustion in a plurality of zones (or stages), where each stage is characterized by a temperature in that stage, a temperature of the incoming oxygen-containing gas, an oxygen content of the incoming gas, a gas flow rate and a duration of exposure of the coked catalyst to these conditions, in order to obtain more efficient combustion.
  • FIG. 2 can be compared with FIG. 1 relating to the prior art.
  • FIGS. 3 and 4 also show implementations of the invention, FIG. 3 showing a further disposition of the monitoring and control zone and FIG. 4 showing a gas management mode.
  • FIG. 2 shows only the combustion step, namely part A of the regeneration process.
  • used catalyst C to be regenerated is introduced into the top (2) of regeneration vessel E via conduit (1).
  • the catalyst is then introduced into a first combustion zone Z1 via conduits or shafts (3).
  • the catalyst undergoes a first burn or combustion using an oxygen-containing gas G1 introduced via conduit (4).
  • the combustion zones are generally radial, preferably annular in the case of the moving bed shown in FIG. 2, and the bed thus flows in an annular space delimited by two coaxial cylindrical walls, the gas entering via one wall and leaving via the other.
  • flow is continuous. Intermittent flow is also possible.
  • gas G'1 is extracted from the zone via conduit (5).
  • Catalyst C drops via shafts (6) or other conduits into the second combustion zone Z2 into which an oxygen-containing gas G2 is introduced via a pipe (7).
  • combustion zones Z1 and Z2 are successive and adjacent, i.e., the catalyst leaving combustion zone Z1 passes directly into combustion zone Z2 and undergoes no treatment between the two zones.
  • Combustion zones Z1 and Z2 are physically separated so as to allow catalyst to pass but to prevent the passage of gas, for example the passage of gases G'1 to Z2.
  • a plate (8) is positioned between zones Z1 and Z2 over the whole cross section of regeneration vessel E, with the exception of sections reserved for the passage of catalyst (shafts or other conduits).
  • catalyst shafts or other conduits
  • gas G'2 is extracted from the zone via conduit (9); more generally the gas from the last combustion zone is extracted from the vessel. Catalyst C then drops via shafts or other conduits (10) to an oxychlorination zone which is not shown here. After combustion, it is treated in known manner to ensure regeneration (oxychlorination, calcining). It should also be noted that, preferably, the gases from the oxychlorination zone are extracted from the oxychlorination zone to prevent their passage into the last zone of the combustion step. Thus no chlorine or chlorinated compound is introduced into the gases entering combustion zones Z1 and Z2.
  • FIG. 2 shows two successive combustion zones, the number of combustion zones being selected by the skilled person as a function of the unit to be designed. They are arranged and operated in the same manner as the zones described above.
  • At least part, preferably all, of gas G'1 leaving zone Z1 is introduced into zone Z2 with gas G2, or after optional oxygen addition to form gas G2; this disposition allows maximum use of the remaining oxygen and minimum addition of oxygen.
  • This separate management of the gases in each combustion zone means that the incoming and outgoing gas temperatures are precisely known at any time along with their oxygen contents. In addition to maximum oxygen use, this management enables coke combustion to be controlled by controlling the operating conditions in each zone.
  • this is followed by a combustion completion monitoring and control operation in a final zone of the combustion step.
  • this operation is carried out in the lower portion (in the direction of catalyst flow) of the last combustion zone Z2, this lower portion thus constituting a monitoring and control zone FC.
  • monitoring and control zone FC is a zone which is not included in the last combustion zone Z2.
  • Monitoring and control zone FC is distinguished from a combustion zone in that in zone FC, the approximate oxygen consumption is less than 10% of the incoming oxygen.
  • the temperature there advantageously remains substantially constant (variation of 3% maximum, preferably 2% maximum) excluding measurement errors and heat losses.
  • An oxygen-containing gas G3 enters zone FC via conduit (11) in FIG. 2 (and 27 in FIG. 3), the gas being extracted via conduit (9) in FIG. 2 after passage through zone FC via which gas G'2 which has traversed combustion zone Z2 is also evacuated, or via conduit 28 in FIG. 3, independently of G'2.
  • the skilled person will select suitable means for measuring the oxygen consumption in zone FC.
  • the variation in the oxygen content between the inlet and outlet from zone FC can be measured from a variation in the inlet content (at the same total gas flow rate) and the variation in the content at the zone outlet.
  • the oxygen consumption in zone FC must be small (less than 2-3%).
  • a further method is to provide means for measuring the temperature and/or oxygen content either in the outgoing gas (for example in FIG. 3 where the gas leaves independently of the other gases from the combustion step) or at the wall via which the gas leaves zone FC (FIG. 2, for example).
  • Means for measuring the temperature of the catalytic bed or the catalyst entering and leaving the monitoring and control zone can also be used.
  • At least one operating condition in at least one combustion zone is modified so as to correct the difference.
  • the oxygen content and/or the temperature of the inlet gas could be modified.
  • the operating conditions are selected for each zone and strictly controlled in each zone (in contrast to the prior art) so as to reduce any deleterious effect of combustion on the catalyst by as much as possible.
  • the products formed by this exothermic reaction are principally carbon dioxide and water.
  • the conditions brought about by this combustion are unquestionably those which are the most favourable for ageing or degradation of the catalyst.
  • the presence of water at a high temperature is responsible for a gradual change in the porous support of the catalyst.
  • the specific surface area of a fresh catalyst is close to 250 m 2 /g. At the end of its life, this value falls to below 100 m 2 /g.
  • the quality of combustion is a function of a number of parameters:
  • the oxygen content of the gas which affects the temperature rise in the bed, and thus whether or not the catalyst changes; it also favours the oxygen diffusion rate in the particle;
  • the oxygen supplied is theoretically entirely consumed, if the temperature of the gas and the oxygen content are sufficient to initiate the reaction. At that moment, a portion of the coke is very easily and rapidly burned off.
  • this difficulty can be due to a number of reasons, among them:
  • the coke deposited near to the metallic phase of the catalyst is more hydrogenated than coke accumulated on the catalyst support;
  • the size of the coke clusters in a thin layer, it bums faster than when it is in large clusters.
  • each is characterized by a temperature threshold above which the reaction can initiate satisfactorily and be completed.
  • a number of operating temperatures can be defined;
  • coke with different burning rates for example: surface coke and core coke.
  • the first is consumed more rapidly in depleted oxygen.
  • the second is less accessible and is "harder" to bum; it constitutes the last portion of the coke to be eliminated, and can be burned in an excess of oxygen if it is considered that there are no risks of combustion runaway. It is thus possible to use a high oxygen content and a higher temperature to encourage the combustion reaction of this hard coke.
  • the present invention proposes conditions for multi-staged coke combustion carried out in the steps described above.
  • Each stage (zone) receives at least one oxygen-containing gas at:
  • a temperature T in the range 350° C. to 600° C., preferably 400° C. to 600° C.;
  • each zone has a volume V corresponding to a catalyst residence time of 5 min to 3 hours.
  • the inlet temperature of the oxygen-containing gas and the oxygen content are such that:
  • the maximum temperature at the bed outlet is less than a maximum allowable value, depending on the materials used (for example 770° C. for a low alloy steel);
  • the maximum temperature elevation between the bed inlet and outlet is less than 200° C., preferably of the order of 100° C.;
  • the temperature in the zone is at least 350° C., advantageously at least 400° C. and less than 600° C., preferably less than 580° C. and more preferably at most 550° C.;
  • the temperature in the zone is higher than the temperature in the immediately preceding zone.
  • the temperature T2 is higher than T1 in zone Z1.
  • T2 of the gas G2 entering the second zone is advantageously higher than that T1 of the gas G1 entering the first zone, and T3 is higher than T2 (T3: temperature in monitoring and control zone).
  • zone FC gas at a temperature which is at least equal to that at the end of combustion in the last combustion zone enters zone FC:
  • the oxygen content of the gas introduced also increases with the zone number which the catalyst enters, and the monitoring and control zone corresponds to the highest oxygen content (quantity higher than that of the gases entering the upstream zones).
  • FIG. 3 illustrates the operating conditions of each zone and the gas management.
  • a moving bed of catalyst C successively traverses zones Z1, Z2 and Z3 with temperatures T1, T2 and T3.
  • volume of these zones reduces in the direction of catalyst flow.
  • Volumes V1, V2 and V3 respectively of zones Z1, Z2 and Z3 are such that V1 ⁇ V2 ⁇ V3. Different volumes are selected in this way but equal volumes or volumes which are different in another way can also be envisaged.
  • a compressor (29) supplies a total gas stream divided into three streams supplying zones Z1, Z2 and Z3.
  • An oxygen analyser and a temperature sensor are located in each gas stream so that the oxygen content and temperature can be adjusted if necessary to satisfy specifications.
  • Oxygen is supplied via pipes 21, 22 and 23 respectively for each gas stream, and the temperature is adjusted by means 24, 25 and 26 respectively (ovens in FIG. 3).
  • gases G1, G2 and G3 respectively enter zones Z1, Z2 and Z3 with an oxygen content and temperature which is in agreement with the specifications.
  • the respective values for gases G1, G2 and G3 are:
  • T1 about 460° C.
  • T2 about 480° C.
  • Gas G'1, G'2 and G'3 respectively leaves each zone.
  • the gases are mixed and at least partially taken up in compressor (29) to be used again for combustion, clearly after at least partial elimination of water and other species from the combustion step, and after possible cooling (by quenching, for example) if necessary.
  • FIG. 3 describes a disposition in which the gases from the combustion and finishing zones are mixed, treated and recycled to the zones as the incoming gas.
  • the gases extracted from at least two zones are collected and re-introduced after possible treatment at least in part into at least one combustion zone after optional addition of oxygen.
  • the aim of the treatment is to eliminate water and other combustion products or "side” products (such as chlorine).
  • FC zone (optionally mixed with the gas from the last combustion zone) at least in part into zone FC and/or at least in part into at least one combustion zone, preferably into the first combustion zone, clearly after optional addition of oxygen to form the gas entering the zone, in order to optimise the oxygen consumption.
  • FIG. 4 shows the invention of FIG. 2 with two combustion zones.
  • Gas G'2 (the effluent from the second combustion zone comprising the monitoring and control zone) is cooled in an exchanger (12), washed in an apparatus (13) to eliminate impurities, in particular chlorinated impurities, and a fraction of this effluent is purged via conduit (14), the remaining effluent being dried in a drier (16), then compressed in a compressor (15) and separated into two fractions.
  • One is sent as gas G1 to the first combustion zone after re-heating (oven 18) and after adding oxygen by a gas (for example air) supplied to conduit (17).
  • the other fraction is re-heated (oven 19), oxygen (for example air) is added via conduit (20), and re-introduced as gas G3 into the monitoring and control zone.
  • Gas G'1 extracted from the first combustion zone is introduced into zone Z2 after optional addition of oxygen via conduit (20').
  • the invention is not limited to this embodiment, and the position of some equipment can be modified (for example, placing the drier after the compressor, preferably for all of the effluent), in some cases to reduce the amount of equipment (for example, oven 18 is not used).
  • the invention also concerns a regeneration vessel for carrying out the process.
  • the vessel comprises at least two radial combustion zones (Z1) and (Z2) disposed in series, at least one conduit (4, 7) for introducing oxygen-containing gas into each combustion zone, at least one conduit (1) for introducing catalyst into the vessel, at least one conduit (3, 6) for transferring catalyst between the zones, at least one conduit (10) for transferring catalyst into the following oxychlorination zone, and at least one conduit (9) for evacuating gases from the combustion zone out of the vessel, conduit (9) being located before the oxychlorination zone, the vessel being characterized in that:
  • separation means are disposed between the combustion zones to allow the passage of catalyst between said zones in the conduits for this purpose but to prevent the passage of gases between said zones;
  • At least one conduit (5, 9) is disposed in each zone to extract the gases after passing through said zone.
  • the lower portion of the last combustion zone (Z2) comprises a combustion completion monitoring and control zone (FC), zone (FC) being provided with at least one conduit (11) for introducing at least one oxygen-containing gas and at least one conduit (9) for extracting the gases after passage through the combustion zone (Z2) and the monitoring and control zone (FC).
  • zone (FC) being provided with at least one conduit (11) for introducing at least one oxygen-containing gas and at least one conduit (9) for extracting the gases after passage through the combustion zone (Z2) and the monitoring and control zone (FC).
  • the last combustion zone (Z2) is followed by a monitoring and control zone (FC) such that a separation means is disposed between the two zones to allow catalyst to pass but to prevent the passage of gas, said monitoring and control zone being provided with a conduit (27) for introducing an oxygen-containing gas and a conduit (28) for evacuating gas.
  • At least one conduit (5) for evacuating gas from a combustion zone is connected to at least one conduit (7) for introducing oxygen-containing gas into the following zone.
  • conduit (28, 9) for evacuating gas from the monitoring and control zone (FC) is connected to conduit (4) for introducing oxygen-containing gas into the first combustion zone (Z1) to recycle at least a portion of the gas from monitoring and control zone (FC) to zone (Z1).
  • At least one conduit for adding oxygen In order to monitor and control the operating conditions in each zone, at least one conduit for adding oxygen, optionally at least one means for re-heating gas, and a system for measuring the temperature, the oxygen content and the flow rate are placed in the conduits (4, 7) for introducing oxygen-containing gas into each zone in the vessel, to monitor and adjust the temperature, oxygen content and flow rate as a function of the operating specifications.

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Abstract

The invention concerns a process for moving bed regeneration of a reforming or aromatic hydrocarbon production catalyst. The catalyst includes a support, at least one noble metal and at least one halogen. The process includes a combustion step in which the catalyst is treated in at least two successive combustion zones. Also, the process includes each combustion zone separated from adjacent combustion zones allowing catalyst to pass and preventing passage of gas, at least one oxygen-containing gas introduced into each zone and produced gases extracted from each zone, and the severity of the operating conditions in each zone increasing in the direction of catalyst flow. Advantageously, the combustion step ends in a zone for monitoring and controlling combustion completion characterized by a low or zero oxygen consumption.

Description

The invention relates to moving bed processes for the production of aromatic compounds, in particular for reforming. More particularly, it concerns the combustion step used during regeneration of a used catalyst and is intended to restore its initial catalytic performances.
BACKGROUND OF THE INVENTION
The catalyst generally comprises a support (for example, formed from at least one refractory oxide, the support possibly also including one or more zeolites), at least one noble metal (preferably platinum), and preferably at least one promoter metal (for example tin or rhenium), at least one halogen and optionally one or more additional elements (such as alkalis, alkaline-earths, lanthanides, silicon, group IVB elements, non noble metals, group IIIA elements, etc.). Catalysts of this type contain platinum, for example, and at least one other metal deposited on a chlorinated alumina support. In general, such catalysts are used to convert naphthenic or paraffinic hydrocarbons, which can be transformed by dehydrocyclisation and/or dehydrogenation, for reforming or for the production of aromatic compounds (for example for the production of benzene, toluene, ortho-meta- or para-xylenes). Such hydrocarbons originate from fractionation of crude oil by distillation or other transformation processes.
Such catalysts have been widely described in the literature.
One way of increasing the yields of such reforming or aromatic compound production processes is to reduce the operating pressures at which the different reactions of importance are carried out. As an example, reforming reactions were carried out at 40 bars 30 years ago; 20 years ago, at 15 bars. Today, reforming reactors usually operate at pressures of less than 10 bars, in particular in the range 3 to 8 bars.
The improvement in desirable reactions due to a reduction in pressure is accompanied by more rapid deactivation of the catalyst by coking. Coke, a high molecular weight compound constituted essentially by carbon and hydrogen, is deposited on the active sites of the catalyst. The H/C molar ratio of the coke formed varies from about 0.3 to 1.0. The carbon and hydrogen atoms form condensed poly-aromatic structures with a variable degree of crystalline organisation, depending on the function and nature of the catalyst and the operating conditions of the reactors. While the selectivity of transformation of the hydrocarbons to coke is very tow, the amounts of coke accumulated on the catalyst can be large. Typically, for fixed bed units, such amounts are in the range 2.0% to 20.0% to 25.5% by weight. For circulating bed units, such amounts are below 10.0% by weight.
Coke deposition, which is more rapid at low pressure, also requires more rapid regeneration of the catalyst. Current regeneration cycles have become as short as 2-3 days.
Commonly assigned European patent EP-A-0 378 482 discloses a continuous process for regenerating a reforming or aromatic compound production catalyst which can overcome the inherent disadvantages of shorter and shorter cycles. One of the regeneration steps is oxychlorination of the catalyst. The present invention concerns this step.
In EP-A-0 378 482, the used catalyst slowly travels from top to bottom in a regeneration vessel where it meets, in succession, a first radial moving bed combustion zone, a second radial moving bed combustion zone, an axial moving bed oxychlorination zone and an axial moving bed calcining zone, and:
a) in the first combustion zone, the catalyst is treated at a pressure of 3 to 8 bars, substantially equal to that in the first reforming reactor, at a temperature in the range 350° C. to 450° C., using a combustion gas based on an inert gas circulating as a co-current to the catalyst, comprising 0.01% to 1% of oxygen by volume, the combustion gas originating from a zone for washing the gases from the combustion, oxychlorination and calcining steps;
b) in a second combustion zone, the catalyst arriving directly from the first combustion zone is treated at a pressure of 3 to 8 bars, substantially equal to that in the first reactor, at a temperature which is higher by at least 20° C. than the temperature in the first combustion zone, in the presence of gases originating from the first combustion zone and in the presence of an inert makeup gas to which up to 20% by volume of oxygen is added so that the catalyst is in contact with a gas comprising 0.01% to 1% by volume of oxygen, the gases circulating as a co-current with the catalyst.
The catalyst is then sent to the oxychlorination zone.
In order to present the prior art more clearly, FIG. 1 shows a figure from EP-A-0 378 482 which shows the catalyst supplied via pipe (17a), stored in zone (20) then passing to the regeneration stage via pipes (9) into a first combustion zone (101) then into a second combustion zone (105). Combustion is carried out by injecting a gas charged with oxygen (0.01-1% by volume) and if necessary, a supplemental supply (104) of an inert gas charged with oxygen or air. The combustion step ensemble corresponds to part A of FIG. 1.
We have established that, during operation of this process, good knowledge of the combustion, and thus of its progress and its control, are guarantees of proper operation of the unit and good regeneration quality. We have thus sought to improve combustion monitoring and control. The process proposed in the present patent application can obtain this result by separate management of the gases in each zone, thus controlling the conditions in each combustion zone and preferably terminating combustion by monitoring and controlling combustion completion.
More precisely, the process of the invention is a process for regenerating a moving bed of catalyst for reforming or for aromatic hydrocarbon production, the catalyst comprising a support, at least one noble metal and at least one halogen, the process comprising a combustion step treating the catalyst in at least two successive combustion zones, the process being characterized in that:
each combustion zone is separated from the adjacent combustion zones so as to allow catalyst to pass and to prevent the passage of gas;
at least one oxygen-containing gas is introduced into each zone, and the gases produced are extracted from each zone;
the severity of the operating conditions in each zone increases in the direction of flow of the catalyst.
Preferably, at least a portion, preferably all, of the gas extracted from one combustion zone is sent to the next zone (in the direction of catalyst flow) with possible oxygen addition (air, for example).
In general, the operating conditions are rendered more severe by increasing the temperature and/or the oxygen content of the incoming gas. Preferably, for each zone the oxygen content in the incoming gas is in the range 0.01% to 2%, the temperature of the inlet gas is in the range 350-600° C., the residence time of the catalyst in one zone is in the range 5 min to 3 hours and the WHSV (hourly mass flow rate of gas/mass of catalyst in contact with the gas) is in the range 1-50 h-1.
The combustion step advantageously ends with a final zone for controlling and monitoring combustion completion in which the oxygen consumption is approximately less than 10% of the oxygen entering that zone. The temperature is preferably substantially constant.
The monitoring and control zone is preferably located in the lower portion of the last combustion zone, thus after the flame front.
Further, a gas containing oxygen in an amount which is higher than that of the gas entering the upstream levels (in the direction of flow of the catalyst) is introduced into the control and monitoring zone.
Thus the present invention defines combustion in a plurality of zones (or stages), where each stage is characterized by a temperature in that stage, a temperature of the incoming oxygen-containing gas, an oxygen content of the incoming gas, a gas flow rate and a duration of exposure of the coked catalyst to these conditions, in order to obtain more efficient combustion.
The description of the invention will be easily followed by referring to FIG. 2, which can be compared with FIG. 1 relating to the prior art.
FIGS. 3 and 4 also show implementations of the invention, FIG. 3 showing a further disposition of the monitoring and control zone and FIG. 4 showing a gas management mode.
FIG. 2 shows only the combustion step, namely part A of the regeneration process.
In conventional fashion, used catalyst C to be regenerated is introduced into the top (2) of regeneration vessel E via conduit (1).
The catalyst is then introduced into a first combustion zone Z1 via conduits or shafts (3). In this zone, the catalyst undergoes a first burn or combustion using an oxygen-containing gas G1 introduced via conduit (4).
The combustion zones are generally radial, preferably annular in the case of the moving bed shown in FIG. 2, and the bed thus flows in an annular space delimited by two coaxial cylindrical walls, the gas entering via one wall and leaving via the other.
For a moving bed of catalyst, flow is continuous. Intermittent flow is also possible.
After passage through this first combustion zone, gas G'1 is extracted from the zone via conduit (5).
Catalyst C drops via shafts (6) or other conduits into the second combustion zone Z2 into which an oxygen-containing gas G2 is introduced via a pipe (7).
In accordance with the invention, combustion zones Z1 and Z2 are successive and adjacent, i.e., the catalyst leaving combustion zone Z1 passes directly into combustion zone Z2 and undergoes no treatment between the two zones. Combustion zones Z1 and Z2 are physically separated so as to allow catalyst to pass but to prevent the passage of gas, for example the passage of gases G'1 to Z2.
The skilled person will select the most suitable means to carry out this function. In the implementation shown in FIG. 2, a plate (8) is positioned between zones Z1 and Z2 over the whole cross section of regeneration vessel E, with the exception of sections reserved for the passage of catalyst (shafts or other conduits). Of course, a little gas G'1 will pass into zone Z2 with the catalyst in the shafts (6), but it is only a minor portion of the gas.
After passage through the second combustion zone, gas G'2 is extracted from the zone via conduit (9); more generally the gas from the last combustion zone is extracted from the vessel. Catalyst C then drops via shafts or other conduits (10) to an oxychlorination zone which is not shown here. After combustion, it is treated in known manner to ensure regeneration (oxychlorination, calcining). It should also be noted that, preferably, the gases from the oxychlorination zone are extracted from the oxychlorination zone to prevent their passage into the last zone of the combustion step. Thus no chlorine or chlorinated compound is introduced into the gases entering combustion zones Z1 and Z2.
FIG. 2 shows two successive combustion zones, the number of combustion zones being selected by the skilled person as a function of the unit to be designed. They are arranged and operated in the same manner as the zones described above.
In an advantageous embodiment, at least part, preferably all, of gas G'1 leaving zone Z1 is introduced into zone Z2 with gas G2, or after optional oxygen addition to form gas G2; this disposition allows maximum use of the remaining oxygen and minimum addition of oxygen.
This separate management of the gases in each combustion zone means that the incoming and outgoing gas temperatures are precisely known at any time along with their oxygen contents. In addition to maximum oxygen use, this management enables coke combustion to be controlled by controlling the operating conditions in each zone.
Preferably, this is followed by a combustion completion monitoring and control operation in a final zone of the combustion step.
In the implementation of FIG. 2, this operation is carried out in the lower portion (in the direction of catalyst flow) of the last combustion zone Z2, this lower portion thus constituting a monitoring and control zone FC.
In a further implementation shown in FIG. 3, monitoring and control zone FC is a zone which is not included in the last combustion zone Z2.
Monitoring and control zone FC is distinguished from a combustion zone in that in zone FC, the approximate oxygen consumption is less than 10% of the incoming oxygen. The temperature there advantageously remains substantially constant (variation of 3% maximum, preferably 2% maximum) excluding measurement errors and heat losses.
An oxygen-containing gas G3 enters zone FC via conduit (11) in FIG. 2 (and 27 in FIG. 3), the gas being extracted via conduit (9) in FIG. 2 after passage through zone FC via which gas G'2 which has traversed combustion zone Z2 is also evacuated, or via conduit 28 in FIG. 3, independently of G'2.
The skilled person will select suitable means for measuring the oxygen consumption in zone FC. As an example, the variation in the oxygen content between the inlet and outlet from zone FC can be measured from a variation in the inlet content (at the same total gas flow rate) and the variation in the content at the zone outlet. In general, if the operation of the preceding stages is correct, the oxygen consumption in zone FC must be small (less than 2-3%).
A further method is to provide means for measuring the temperature and/or oxygen content either in the outgoing gas (for example in FIG. 3 where the gas leaves independently of the other gases from the combustion step) or at the wall via which the gas leaves zone FC (FIG. 2, for example).
Means for measuring the temperature of the catalytic bed or the catalyst entering and leaving the monitoring and control zone can also be used.
Thus a simple means for monitoring and controlling the correct operation of the combustion stages is provided, and independent management of the gases of each stage enables combustion faults to be remedied rapidly and easily by varying the temperature or the oxygen content in one or more zones.
If a comparison of oxygen contents or the gas and/or catalyst temperatures leads to variations which are beyond allowable values for the process (less than 10% for oxygen and at most 3% for the temperature), then at least one operating condition in at least one combustion zone is modified so as to correct the difference. The oxygen content and/or the temperature of the inlet gas could be modified.
The operating conditions are selected for each zone and strictly controlled in each zone (in contrast to the prior art) so as to reduce any deleterious effect of combustion on the catalyst by as much as possible.
The products formed by this exothermic reaction are principally carbon dioxide and water. The conditions brought about by this combustion are unquestionably those which are the most favourable for ageing or degradation of the catalyst. In particular, the presence of water at a high temperature is responsible for a gradual change in the porous support of the catalyst. Typically, the specific surface area of a fresh catalyst is close to 250 m2 /g. At the end of its life, this value falls to below 100 m2 /g.
The quality of combustion is a function of a number of parameters:
the temperature of the incoming oxygen-containing gas, sufficient to initiate the reaction and which accelerates the rate of this reaction;
the oxygen content of the gas, which affects the temperature rise in the bed, and thus whether or not the catalyst changes; it also favours the oxygen diffusion rate in the particle;
the quantity of oxygen, which determines the quantity of coke which can be burned.
In the first phases (or moments) of combustion, the oxygen supplied is theoretically entirely consumed, if the temperature of the gas and the oxygen content are sufficient to initiate the reaction. At that moment, a portion of the coke is very easily and rapidly burned off.
We have established that coke which is more difficult to burn can remain: at the temperature at which the first portion of coke is easily burned, a very long time is required to eliminate the other portion.
According to the inventors, this difficulty can be due to a number of reasons, among them:
the presence of different types of coke characterized by different initiation temperatures, different crystalline organisations, and different H(C ratios;
localisation of coke: the coke deposited near to the metallic phase of the catalyst is more hydrogenated than coke accumulated on the catalyst support;
diffusion problems: coke on the surface of the catalyst particle burns more easily than that in the particle core. An oxygen diffusion problem is added to the chemical reactivity problems for coke deposited in the core of the catalyst grain;
the size of the coke clusters: in a thin layer, it bums faster than when it is in large clusters.
These reasons imply that there is a multitude of coke species:
coke with different initiation temperatures: each is characterized by a temperature threshold above which the reaction can initiate satisfactorily and be completed. In this case, a number of operating temperatures can be defined;
coke with different burning rates, for example: surface coke and core coke. The first is consumed more rapidly in depleted oxygen. The second is less accessible and is "harder" to bum; it constitutes the last portion of the coke to be eliminated, and can be burned in an excess of oxygen if it is considered that there are no risks of combustion runaway. It is thus possible to use a high oxygen content and a higher temperature to encourage the combustion reaction of this hard coke.
Instead of using identical gas conditions which are adapted for an "average" coke as in the prior art, the present invention proposes conditions for multi-staged coke combustion carried out in the steps described above.
Each stage (zone) receives at least one oxygen-containing gas at:
a WHSV in the range 1 to 50 h-1, preferably 10-40 h-1, more preferably 15-35 h-1 ;
a temperature T in the range 350° C. to 600° C., preferably 400° C. to 600° C.;
an oxygen content of at most 2%, preferably 0.5-1.5%, and generally over 0.5%;
each zone has a volume V corresponding to a catalyst residence time of 5 min to 3 hours.
For each zone, the inlet temperature of the oxygen-containing gas and the oxygen content are such that:
the maximum temperature at the bed outlet is less than a maximum allowable value, depending on the materials used (for example 770° C. for a low alloy steel);
the maximum temperature elevation between the bed inlet and outlet is less than 200° C., preferably of the order of 100° C.;
the temperature in the zone is at least 350° C., advantageously at least 400° C. and less than 600° C., preferably less than 580° C. and more preferably at most 550° C.;
the temperature in the zone is higher than the temperature in the immediately preceding zone. Thus in zone Z2, the temperature T2 is higher than T1 in zone Z1.
These ever higher temperatures result from transferring hot catalyst from the preceding zone, from introducing hot oxygen-containing gas, from the exothermal combustion reaction which develops, and from the increasing severity of the operating conditions.
In order to guarantee correct combustion, hotter and hotter gases are preferably introduced into the zones encountered during catalyst flow. Thus temperature T2 of the gas G2 entering the second zone is advantageously higher than that T1 of the gas G1 entering the first zone, and T3 is higher than T2 (T3: temperature in monitoring and control zone).
More precisely, gas at a temperature which is at least equal to that at the end of combustion in the last combustion zone enters zone FC:
the oxygen content of the gas introduced also increases with the zone number which the catalyst enters, and the monitoring and control zone corresponds to the highest oxygen content (quantity higher than that of the gases entering the upstream zones).
the embodiment shown in FIG. 3 illustrates the operating conditions of each zone and the gas management.
In regeneration vessel E, a moving bed of catalyst C successively traverses zones Z1, Z2 and Z3 with temperatures T1, T2 and T3.
The volume of these zones reduces in the direction of catalyst flow. Volumes V1, V2 and V3 respectively of zones Z1, Z2 and Z3 are such that V1<V2<V3. Different volumes are selected in this way but equal volumes or volumes which are different in another way can also be envisaged.
A compressor (29) supplies a total gas stream divided into three streams supplying zones Z1, Z2 and Z3.
An oxygen analyser and a temperature sensor are located in each gas stream so that the oxygen content and temperature can be adjusted if necessary to satisfy specifications.
Oxygen is supplied via pipes 21, 22 and 23 respectively for each gas stream, and the temperature is adjusted by means 24, 25 and 26 respectively (ovens in FIG. 3).
Thus gases G1, G2 and G3 respectively enter zones Z1, Z2 and Z3 with an oxygen content and temperature which is in agreement with the specifications.
As an example, the respective values for gases G1, G2 and G3 are:
T1 about 460° C.;
T2 about 480° C.
T3 about 520° C.
And for oxygen contents, respectively:
O1 about 0.8
O2 about 0.8
O3 about 1.1.
Gas G'1, G'2 and G'3 respectively leaves each zone. In the embodiment of FIG. 3, the gases are mixed and at least partially taken up in compressor (29) to be used again for combustion, clearly after at least partial elimination of water and other species from the combustion step, and after possible cooling (by quenching, for example) if necessary.
FIG. 3 describes a disposition in which the gases from the combustion and finishing zones are mixed, treated and recycled to the zones as the incoming gas.
More generally, the gases extracted from at least two zones are collected and re-introduced after possible treatment at least in part into at least one combustion zone after optional addition of oxygen.
It is preferably recycled to the first combustion zone.
The aim of the treatment is to eliminate water and other combustion products or "side" products (such as chlorine).
It is also important to re-introduce the gas from the FC zone (optionally mixed with the gas from the last combustion zone) at least in part into zone FC and/or at least in part into at least one combustion zone, preferably into the first combustion zone, clearly after optional addition of oxygen to form the gas entering the zone, in order to optimise the oxygen consumption.
In this case, one preferred embodiment for managing the gases is that shown in FIG. 4. This shows the invention of FIG. 2 with two combustion zones.
Gas G'2 (the effluent from the second combustion zone comprising the monitoring and control zone) is cooled in an exchanger (12), washed in an apparatus (13) to eliminate impurities, in particular chlorinated impurities, and a fraction of this effluent is purged via conduit (14), the remaining effluent being dried in a drier (16), then compressed in a compressor (15) and separated into two fractions. One is sent as gas G1 to the first combustion zone after re-heating (oven 18) and after adding oxygen by a gas (for example air) supplied to conduit (17). The other fraction is re-heated (oven 19), oxygen (for example air) is added via conduit (20), and re-introduced as gas G3 into the monitoring and control zone. Gas G'1 extracted from the first combustion zone is introduced into zone Z2 after optional addition of oxygen via conduit (20').
The invention is not limited to this embodiment, and the position of some equipment can be modified (for example, placing the drier after the compressor, preferably for all of the effluent), in some cases to reduce the amount of equipment (for example, oven 18 is not used).
The invention also concerns a regeneration vessel for carrying out the process. The vessel comprises at least two radial combustion zones (Z1) and (Z2) disposed in series, at least one conduit (4, 7) for introducing oxygen-containing gas into each combustion zone, at least one conduit (1) for introducing catalyst into the vessel, at least one conduit (3, 6) for transferring catalyst between the zones, at least one conduit (10) for transferring catalyst into the following oxychlorination zone, and at least one conduit (9) for evacuating gases from the combustion zone out of the vessel, conduit (9) being located before the oxychlorination zone, the vessel being characterized in that:
separation means are disposed between the combustion zones to allow the passage of catalyst between said zones in the conduits for this purpose but to prevent the passage of gases between said zones;
and at least one conduit (5, 9) is disposed in each zone to extract the gases after passing through said zone.
In a preferred embodiment (FIG. 2), the lower portion of the last combustion zone (Z2) comprises a combustion completion monitoring and control zone (FC), zone (FC) being provided with at least one conduit (11) for introducing at least one oxygen-containing gas and at least one conduit (9) for extracting the gases after passage through the combustion zone (Z2) and the monitoring and control zone (FC).
In a further preferred embodiment (FIG. 3), the last combustion zone (Z2) is followed by a monitoring and control zone (FC) such that a separation means is disposed between the two zones to allow catalyst to pass but to prevent the passage of gas, said monitoring and control zone being provided with a conduit (27) for introducing an oxygen-containing gas and a conduit (28) for evacuating gas.
Preferably, at least one conduit (5) for evacuating gas from a combustion zone is connected to at least one conduit (7) for introducing oxygen-containing gas into the following zone.
Advantageously, conduit (28, 9) for evacuating gas from the monitoring and control zone (FC) is connected to conduit (4) for introducing oxygen-containing gas into the first combustion zone (Z1) to recycle at least a portion of the gas from monitoring and control zone (FC) to zone (Z1).
In order to monitor and control the operating conditions in each zone, at least one conduit for adding oxygen, optionally at least one means for re-heating gas, and a system for measuring the temperature, the oxygen content and the flow rate are placed in the conduits (4, 7) for introducing oxygen-containing gas into each zone in the vessel, to monitor and adjust the temperature, oxygen content and flow rate as a function of the operating specifications.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
The entire disclosure of all applications, patents and publications, cited above and below, and of corresponding French application No. 97/04.663, are hereby incorporated by reference.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims (13)

What is claimed is:
1. A process for regenerating a moving bed of catalyst flowing in a selected direction for reforming or for aromatic hydrocarbon production, said catalyst comprising a support, at least one noble metal and at least one halogen, the process including a combustion step of treating the catalyst in at least two successive combustion zones, the process comprising:
maintaining each combustion zone separate from adjacent combustion zones to allow catalyst to pass between adjacent zones and to prevent the passage of gas from one zone to an adjacent zone;
introducing at least one oxygen-containing gas into each zone, and extracting the gases produced from each zone; and
increasing the severity of the operating conditions in each zone separately in the direction of catalyst flow.
2. A process according to claim 1, in which at least a portion of the gas extracted from one combuston zone is sent to an adjacent combustion zone in the direction of catalyst flow with optional oxygen addition.
3. A process according to claim 1, in which all of the gas extracted from one combustion zone is sent to the successive combustion zone, with optional oxygen addition.
4. A process according to claim 1 in which the temperature and optionally the oxygen content of gas entering each successive combustion zone are increased.
5. A process according to claim 1, in which for each zone the oxygen content of the introduced gas entering the combustion zone is in the range 0.01% to 2%, the temperature of the introduced oxygen-containing gas is in the range 350-600° C., the residence time of the catalyst in one combustion zone is in the range 5 min to 3 hours and the hourly mass flow rate of gas/mass of catalyst in contact with the gas is in the range of 1-50 h-1.
6. A process according to claim 1, in which the combustion step ends with a final zone for controlling and monitoring the end of combustion in which the oxygen consumption is less than 10% of the oxygen entering that zone.
7. A process according to claim 6, in which the temperature is substantially constant in the monitoring and control zone.
8. A process according to claim 4, in which the monitoring and control zone is located in the lower portion of the last combustion zone.
9. A process according to claim 6, in which an oxygen-containing gas is introduced into the gas in the monitoring and control zone in a quantity which is higher than that of the gases entering upstream levels of the catalyst flow in the direction of catalyst flow.
10. A process according to claim 6, in which at least a portion of the gas from the monitoring and control zone is re-introduced into the first combustion zone.
11. A process according to claim 6, in which at least a portion of the gas from the monitoring and control zone is re-introduced into the monitoring and control zone.
12. A process according to claim 1, in which gases extracted from at least two zones are collected and re-introduced at least in part into a combustion zone after optional oxygen addition.
13. A process according to claim 1, comprising a combustion step for treating the catalyst in a first combustion zone then in a second combustion zone, wherein the zones are separated so as to allow catalyst to pass and to prevent the passage of the gas, the second combustion zone having a lower portion comprising a combustion completion monitoring and control zone; wherein all the gas extracted from the first combustion zone is sent to the second combustion zone after adding oxygen, and wherein the gas from the second combustion zone is cooled, treated to eliminate the impurities, purged, dried, compressed then separated into two fractions, one fraction, after re-heating and after adding oxygen, being introduced into the first combustion zone and the other fraction being re-heated, oxygen being added and introduced into the monitoring and control zone.
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US20120322649A1 (en) * 2011-06-17 2012-12-20 Uop Llc Processes and apparatuses for regenerating catalyst particles
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US7780928B2 (en) * 2007-10-29 2010-08-24 Leon Yuan Method and apparatus for improving radial flow moving bed regeneration/reaction system performance
US20090110616A1 (en) * 2007-10-29 2009-04-30 Leon Yuan Method and apparatus for improving radial flow moving bed regeneration/reaction system performance
US20100160702A1 (en) * 2008-12-23 2010-06-24 Chevron Phillips Chemical Company Lp Methods of Preparing an Aromatization Catalyst
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US9421529B2 (en) 2008-12-23 2016-08-23 Chevron Philips Chemical Company Lp Methods of reactivating an aromatization catalyst
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US8664144B2 (en) 2008-12-23 2014-03-04 Chevron Phillips Chemical Company Lp Methods of reactivating an aromatization catalyst
US8664145B2 (en) 2008-12-23 2014-03-04 Chevron Phillips Chemical Company Lp Methods of preparing an aromatization catalyst
US8901025B2 (en) 2010-03-24 2014-12-02 IFP Energies Nouvelles Catalyst regeneration zone divided into sectors for regenerative catalytic units
CN103068483B (en) * 2010-07-30 2015-04-01 拜耳知识产权有限责任公司 Process for restoring catalyst activity
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US8716161B2 (en) 2012-03-05 2014-05-06 Chevron Phillips Chemical Company Methods of regenerating aromatization catalysts
US8912108B2 (en) 2012-03-05 2014-12-16 Chevron Phillips Chemical Company Lp Methods of regenerating aromatization catalysts
US9421530B2 (en) 2012-03-05 2016-08-23 Chevron Phillips Chemical Company Lp Methods of regenerating aromatization catalysts
US9174895B2 (en) 2012-03-05 2015-11-03 Chevron Phillips Chemical Company Lp Methods of regenerating aromatization catalysts
US9943837B2 (en) 2012-03-05 2018-04-17 Chevron Phillips Chemical Company Lp Methods of regenerating aromatization catalysts
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US9314786B2 (en) 2012-07-25 2016-04-19 Axens Reactor for continuous catalyst regeneration with a perforated box for mixing and distributing gases in the oxychlorination zone
US9295985B2 (en) 2012-07-25 2016-03-29 Axens Continuous catalyst regeneration reactor with a chamber for mixing gas and distributing gas in the oxychlorination zone
US9387467B2 (en) 2012-09-26 2016-07-12 Chevron Phillips Chemical Company Lp Aromatization catalysts with high surface area and pore volume
US10183284B2 (en) 2012-09-26 2019-01-22 Chevron Phillips Chemical Company Lp Aromatization catalysts with high surface area and pore volume
US9708551B2 (en) 2014-09-10 2017-07-18 IFP Energies Nouvelles Regenerator for catalysts
US9708552B2 (en) 2014-09-10 2017-07-18 IFP Energies Nouvelles Regenerator for regenerating catalysts under different operating conditions

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